US4656007A - Programmable automatic means for the deposition in a precise position of a minute, precise quantity of liquid on an analytical support - Google Patents

Programmable automatic means for the deposition in a precise position of a minute, precise quantity of liquid on an analytical support Download PDF

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Publication number
US4656007A
US4656007A US06/779,578 US77957885A US4656007A US 4656007 A US4656007 A US 4656007A US 77957885 A US77957885 A US 77957885A US 4656007 A US4656007 A US 4656007A
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United States
Prior art keywords
syringe
support
needle
analytical
holder
Prior art date
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Expired - Fee Related
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US06/779,578
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English (en)
Inventor
Marc Douchy
Pierre Lohez
Jean-Guy Malecot
Gilbert Retali
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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Assigned to COMMISSARIAT A L'ENERGIE ATOMIQUE reassignment COMMISSARIAT A L'ENERGIE ATOMIQUE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: DOUCHY, MARC, LOHEZ, PIERRE, MALECOT, JEAN-GUY, RETALI, GILBERT
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Publication of US4656007A publication Critical patent/US4656007A/en
Anticipated expiration legal-status Critical
Assigned to BANK OF AMERICA, N.A. reassignment BANK OF AMERICA, N.A. SECURITY AGREEMENT Assignors: XYRON, INC.
Expired - Fee Related legal-status Critical Current

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/10Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices
    • G01N35/1009Characterised by arrangements for controlling the aspiration or dispense of liquids
    • G01N35/1016Control of the volume dispensed or introduced
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/02Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor using a plurality of sample containers moved by a conveyor system past one or more treatment or analysis stations
    • G01N35/04Details of the conveyor system
    • G01N2035/0439Rotary sample carriers, i.e. carousels
    • G01N2035/0441Rotary sample carriers, i.e. carousels for samples
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/10Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices
    • G01N2035/1027General features of the devices
    • G01N2035/103General features of the devices using disposable tips
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/10Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices
    • G01N35/1081Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices characterised by the means for relatively moving the transfer device and the containers in an horizontal plane
    • G01N35/1083Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices characterised by the means for relatively moving the transfer device and the containers in an horizontal plane with one horizontal degree of freedom
    • G01N2035/1086Cylindrical, e.g. variable angle
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/10Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices
    • G01N35/1009Characterised by arrangements for controlling the aspiration or dispense of liquids
    • G01N35/1011Control of the position or alignment of the transfer device
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00Chemistry: analytical and immunological testing
    • Y10T436/11Automated chemical analysis
    • Y10T436/113332Automated chemical analysis with conveyance of sample along a test line in a container or rack
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00Chemistry: analytical and immunological testing
    • Y10T436/25Chemistry: analytical and immunological testing including sample preparation
    • Y10T436/2575Volumetric liquid transfer

Definitions

  • the present invention relates to a programmable automatic means for the deposition in a precise position of a minute and precise quantity of liquid on an analytical or analysis support.
  • This automatic means is more particularly intended for supplying with successive samples deposited on supports to equipment for the successive analysis of a solution when the solution quantity to be deposited is of small volume (1 to 20 microliters).
  • This automatic means is also suitable for supplying equipment for analyzing solution samples, when it is not possible or not wished to use more than a small amount of the solution, which can e.g. be the case in medical analysis.
  • the invention aims at providing a programmable automatic means simultaneously having all the following performance characteristics:
  • the sample must be taken in a minute quantity of just a few small drops, with a high accuracy and total reproducibility of the number of drops;
  • the invention has the essential aim of proposing such a novel, automatic means.
  • the invention relates to a programmable automatic means for carrying out the deposition in a precise position on an analytical support of a precise, variable and reproducible minute quantity of liquid, wherein it comprises in combination:
  • a main support provided with displacement means enabling it to successively occupy at least five positions
  • a piston syringe mounted on the main support and provided with means for displacing said syringe relative to said main support, and means for grasping a hollow solution sampling needle by one of its ends and means for displacing the piston;
  • each hollow needle is new and has a length slightly exceeding the subsequent precise length
  • a cutting device placed in a second position corresponding to the second position of the syringe-holder support for cutting a needle held by said syringe end gripping means to the precise length at a precise point in space, when the syringe-holder support is placed in its second position,
  • a solution sample distributor having several recesses provided with means for successively presenting each recess at a third location corresponding to the third position of the syringe-holder support, each recess serving to receive a solution sample prior to a complete operating cycle of the automatic means,
  • an analysis or analytical support holder provided with displacement means enabling it to occupy three positions, whereof the second corresponds to the fourth position of the syringe-holder support,
  • a new analytical support distributor having a plurality of recesses, provided with means for successively presenting each analytical support at a location corresponding to the first position of said analytical support holder, each recess serving to receive a new analytical support before a complete operating cycle of the automatic means,
  • a receiver for analytical supports following sample deposition having several recesses, provided with means for successively presenting each recess at a location corresponding to the third position of said analytical support holder, each recess of the receiver being left free prior to a complete operating cycle of the automatic means,
  • a used needle extractor placed at a location corresponding to the fifth position of the syringe-holder support
  • This automatic means essentially functions as follows. In its first position, the syringe holder makes the syringe grasp a new hollow needle. In its second position the syringe holder presents the end of said needle to the cutting device, which cuts the needle to a precise length. In the third syringe holder position, the syringe advances towards a recess in the sample distributor and introduces the new hollow needle into it. The syringe piston then moves back in order to such up a precise quantity of the sample solution to be analyzed. The complete syringe then moves back.
  • the accurately cut end of the hollow needle filled with the sample liquid to be analyzed is positioned in a very precise position with respect to a new analytical support, which is then presented by an analytical support holder in the second position.
  • the syringe piston advances stepwise in order to deposit an exact desired and reproducible number of sample drops on the analytical support.
  • the syringe end is freed from the used needle.
  • the analytical support holder takes up, in its first position, a new analytical support.
  • One of the essential features of the automatic means is based on the non-obvious choice made by producing the succession of hollow sampling needles, by successive cutting to the precise length of a sequence of small diameter, hollow tube elements. This overcomes the problem of length variation in commercially produced needles, so that certainty exists regarding the position in space of the needle end, which is indispensable for being able to very accurately position said end with respect to an analytical support.
  • the syring is mounted on the main syringe-holder support via elastic means and the needle grasping end of the syringe is an outwardly widened conical shape and is provided with at least one friction O-ring.
  • each sample distributor recess is a cylindrical recess whose bottom is provided with elastic means for freely receiving small corresponding container containing a sample, and the angle formed with the vertical by the common axis of the small container and its recess is greater than the angle formed with the vertical by the hollow sampling needle axis.
  • FIG. 1 in perspective, all the elements forming the programmable automatic means according to the invention.
  • FIG. 2 diagrammatically, in plan view, said same group of components.
  • FIG. 3 diagrammatically and in section a syringe holder.
  • FIG. 4 diagrammatically and in section a needle distributor.
  • FIG. 5 diagrammatically and in section a device for cutting a hollow sampling needle to a precise length.
  • FIG. 6 diagrammatically and in section the relative positions of the syringe-holder support with respect to the sample distributor and the analytical support holder for the successive operations corresponding to these two positions.
  • thermoionization mass spectrometry For the study of solids by thermoionization mass spectrometry, it is necessary to deposit on one of the filaments of a three-filament support member, small quantities (10 -2 to 10 microgrammes) of the element to be studied.
  • the procedure used consists of placing in an acid solution (generally 0.2N nitric acid) the element to be studied and depositing on the filament chosen a few microliters (1 to 10) of said solution.
  • the solution is deposited in fractions (e.g. 0.5 microliter) whilst evaporating to dryness, between each fraction deposited, by passing an electric current through the filament in question.
  • the filament is heated, by the passage of an electric current, followed by a given procedure for bringing the deposit into the most suitable chemical state for analysis.
  • the two other filaments which are then connected in series, are slightly heated by the passage of an electric current, to prevent any condensation of the product on the surface thereof.
  • This procedure is used in fuel reprocessing plants and then leads to the deposition of active solutions.
  • This automatic means comprises a system of mechanical elements, controlled from a microprocessor card via interface frames.
  • a printer permits a dialogue with the automatic means.
  • the active elements of the automatic means are obviously installed in a tight enclosure (glove box).
  • the elements necessary for the electrical supply, control and command of the robot are placed in an electronic bay.
  • the central part of the automatic means mounted on a workbench 1 is a main support constituted by a turret 2, provided with rotation means enabling it to successively occupy five positions around centre 0 (FIG. 2), resprectively P1, P2, P3, P4 and P5.
  • a syringe holder 3, carrying a syringe 4 and terminated by a needle 5, is mounted in mobile manner on turret 2 so as to permit, for each position of the turret P1, P2, P3, P4 or P5, an advance or return of the syringe 4 and its needle 5 with respect to the different locations of operations to be performed, corresponding to these five positions as will be described hereinafter.
  • the syringe holder is shown in greater detail in FIG. 3, where it is possible to see the turret 2 on which is mounted the syringe holder 3.
  • the latter is mobile on turret 2 for advance and return movements as a result of the action of a motor 6, and a reduction gear 7, actuating a threaded bar 8 controlling said movements of the syringe holder in slides provided for this purpose.
  • the actual syringe 4 is mounted on its syringe holder 3 by elastic means indicated by spring 9.
  • the front end 10 of the syringe has an outwardly widened conical shape and is equipped with two friction O-rings 11. As stated hereinbefore, these means are responsible for the guidance at the syringe entrance of the needle end when the syringe approaches said end, the centering of the needle and its grasping and holding by O-rings 11.
  • the needle head When the advance movement of the syringe towards the needle continues, the needle head finally abuts on the syringe shoulder 12 and a supplementary advance of the syringe leads to a displacement thereof with respect to syringe holder 3 as a result of the compression of spring 9.
  • a geared motor 13 makes it possible to displace piston 14 within syringe 4.
  • the automatic means also comprises a distributor for a plurality of hollow sampling needles 15 in FIGS. 1 and 2 and shown in greater detail in FIG. 4.
  • this distributor essentially comprises a journal 16 having a circular base ring 17 and a circular flange 18 perforated by a respective series of recesses 19 and holes 20 in several positions, e.g. 32 thereof.
  • the needle distributor 15 Prior to a complete operating cycle the automatic means, the needle distributor 15 is loaded with 32 new hollow needles 5, having a length slightly greater than the consequently precise length, as will be shown hereinafter.
  • the gripping of the needle takes place when the central turret 2 is oriented towards its position P1 and as can be desribed relative to FIG. 3.
  • the automatic means also comprises a needle cutting device 21 in FIGS. 1 and 2 and shown in greater detail in FIG. 5.
  • This device cooperates with the syringe holder turret 2, when the latter is oriented in its position P2.
  • the cutting device 21 essentially comprises the rotary cutter 22, driven by a motor 23 mounted on a support 24 and able to move forward or back under the control of a motor 25, driving by a reduction gear 26 a threaded bar 27 controlling the movements thereof.
  • Cutter 22 penetrates and advances in the guidance slot 29 in order to bring about a bevel cut at a precise point in space of the end of needle 5. The cutter then returns to the left position and the syringe holder withdraws to the rear the needle cut to the precise length.
  • the automatic means also comprises a distributor 30 for the successive samples to be analyzed, cf. FIGS. 1 and 2 and diagrammatically shown in section in FIG. 6.
  • This sample distributor which cooperates with the syringe holder 22 when the latter is oriented in its position P3, essentially comprises a vertically axed circular journal 31, provided on its periphery with a plurality, e.g. 32, of cylindrical recesses with an axis inclined by 60° relative to the vertical. Each recess 32 is provided with a flexible elastic coating 33 on its bottom.
  • the liquid sample is oontained in small glass containers 34.
  • the sample distributor 30 is filled with these thirtytwo small containers 34.
  • the relative slope of the axes of needle 5 and containers 34 resting on the elastic bases 33 of recess 32 ensures that the sampling needle end 5 will, at the end of the travel of syringe 4, be positioned at the lowest point of container 34. This ensures the good takeup of sample, even if container 34 only contains a very small amount of this. More specifically, the descent axis of the needle intersects the base plane of container 34 at the bottom point thereof.
  • the syringe piston 14 then rises by n steps, a step corresponding to e.g. 0.5 microliter and the maximum number of steps n being 15, i.e. corresponding to 7.5 microliters.
  • the syringe rises and then moves back.
  • a prior moving back of the piston prior to sampling makes it possible to lower the latter again to a position lower than that at the start of sampling.
  • the needle which abuts against the bottom of the container leads to an elastic moving back of the syringe, but does not modify the position of the needle in the inoperative state.
  • the number of sampling steps is limited by the needle capacity to prevent any pollution of one sample by the preceding samples (needle used once only, the only sampling element in contact with the solution to be deposited).
  • the automatic means is then positioned in position P4 facing an analytical support holder 35 in FIGS. 1, 2 and 6 (to the right of the latter).
  • This analytical support holder 35 is provided with rotation means enabling it to successively occupy a first position P1 (FIG. 2) facing a new analytical support distributor 36.
  • these analytical supports 37 are source support filaments for thermoionization mass spectrometry.
  • the analytical support distributor 36 could be of a type having a journal 38 with a plurality of positions, 32 in this example.
  • Piston 14 drops by one step, forming a drop which touches the filament at the end of needle 5.
  • the syringe 4 rises again leaving a drop on the filament.
  • the filament is heated to evaporate the drop.
  • the syringe is lowered again and so on. If sampling involves n steps, deposition takes place over n+3 steps, so that it is certain that all the solution to be deposited is restored on the filament.
  • the first two descent steps of the piston are used for recovering the mechanical clearances compensating the capillarity phenomena in the needle.
  • the drop only appears at the third step.
  • the reheating required by the operator takes place.
  • the syringe holder 3 and filament holder 35 are then moved back.
  • This receiver has a multi-position journal 40, 32 in the present example, which are successively presented in position P3 of the analytical support holder 35 for receiving the support following sample deposition.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Automatic Analysis And Handling Materials Therefor (AREA)
  • Sampling And Sample Adjustment (AREA)
US06/779,578 1984-10-01 1985-09-24 Programmable automatic means for the deposition in a precise position of a minute, precise quantity of liquid on an analytical support Expired - Fee Related US4656007A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8415048A FR2571147B1 (fr) 1984-10-01 1984-10-01 Automate programmable pour effectuer le depot en position precise sur un support d'analyse d'une infime quantite precise de liquide
FR8415048 1984-10-01

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US4656007A true US4656007A (en) 1987-04-07

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US (1) US4656007A (fr)
EP (1) EP0180494B1 (fr)
JP (1) JPS61262664A (fr)
DE (1) DE3569032D1 (fr)
FR (1) FR2571147B1 (fr)

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US4951512A (en) * 1988-06-23 1990-08-28 Baxter International Inc. System for providing access to sealed containers
DE4004198A1 (de) * 1990-02-12 1991-08-14 Max Planck Gesellschaft Geraet zum dosierten einfuehren einer substanz in eine anzahl von substraten
US5059393A (en) * 1989-01-05 1991-10-22 Eastman Kodak Company Analysis slide positioning apparatus and method for a chemical analyzer
US5085832A (en) * 1990-07-20 1992-02-04 Eastman Kodak Company Dispensing mechanism
US5089229A (en) 1989-11-22 1992-02-18 Vettest S.A. Chemical analyzer
US5171531A (en) * 1989-10-25 1992-12-15 Hewlett-Packard Company Apparatus for automatic delivery of a vial to an automated sampling system
US5250262A (en) 1989-11-22 1993-10-05 Vettest S.A. Chemical analyzer
US5504343A (en) * 1993-08-20 1996-04-02 Compagnie Generale Des Matieres Nucleaires Device for storing cylindrical objects with fast charging and discharging
EP0802413A2 (fr) * 1996-02-21 1997-10-22 bioMerieux Vitek, Inc. Machine d'essai automatique d'échantillons
US5697409A (en) * 1996-02-21 1997-12-16 Biomerieux Vitek, Inc. Diluting and pipetting stations for sample testing machine
US5762873A (en) * 1996-02-21 1998-06-09 Biomerieux Vitek, Inc. Automatic sample testing machine
US6269846B1 (en) 1998-01-13 2001-08-07 Genetic Microsystems, Inc. Depositing fluid specimens on substrates, resulting ordered arrays, techniques for deposition of arrays
US6407858B1 (en) 1998-05-14 2002-06-18 Genetic Microsystems, Inc Focusing of microscopes and reading of microarrays
US6428752B1 (en) 1998-05-14 2002-08-06 Affymetrix, Inc. Cleaning deposit devices that form microarrays and the like
US20020155491A1 (en) * 1990-12-06 2002-10-24 Affymetrix, Inc. Arrays for detecting nucleic acids
US6722395B2 (en) 1998-01-13 2004-04-20 James W. Overbeck Depositing fluid specimens on substrates, resulting ordered arrays, techniques for analysis of deposited arrays
US20040092032A1 (en) * 1991-11-22 2004-05-13 Affymetrix, Inc. Combinatorial strategies for polymer synthesis
US20040142383A1 (en) * 2001-05-15 2004-07-22 Wolfgang Altmeyer Method for qualitative and/or quantitative determination of genus, species, race and/or geographical origin of biological material
US6849462B1 (en) 1991-11-22 2005-02-01 Affymetrix, Inc. Combinatorial strategies for polymer synthesis
US20050036911A1 (en) * 2003-08-12 2005-02-17 Sellers James M. Slide cartridge and reagent test slides for use with a chemical analyzer, and chemical analyzer for same
US20050285049A1 (en) * 1998-03-20 2005-12-29 Montagu Jean I Focusing of microscopes and reading of microarrays
US7442499B2 (en) 1994-06-17 2008-10-28 The Board Of Trustees Of The Leland Stanford Junior University Substrates comprising polynucleotide microarrays
US7625697B2 (en) 1994-06-17 2009-12-01 The Board Of Trustees Of The Leland Stanford Junior University Methods for constructing subarrays and subarrays made thereby
US20100254854A1 (en) * 2007-05-08 2010-10-07 Idexx Laboratories, Inc. Chemical analyzer
US8585989B2 (en) 2003-12-04 2013-11-19 Idexx Laboratories, Inc. Retaining clip for reagent test slides
US20140163366A1 (en) * 1997-12-04 2014-06-12 Bracco Suisse Sa Automatic Liquid Injection System and Method
US9797916B2 (en) 2014-01-10 2017-10-24 Idexx Laboratories, Inc. Chemical analyzer
US10031051B2 (en) * 2008-08-15 2018-07-24 Ctc Analytics Ag Sample deposition device
US10365291B2 (en) * 2015-11-25 2019-07-30 Siemens Healthcare Diagnostics Products Gmbh Method for transferring a liquid volume in an analyzer
US11977091B2 (en) 2020-07-10 2024-05-07 Idexx Laboratories Inc. Point-of-care medical diagnostic analyzer and devices, systems, and methods for medical diagnostic analysis of samples

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CN107677843A (zh) * 2017-09-26 2018-02-09 迈克医疗电子有限公司 试剂容器封闭装置

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US3525264A (en) * 1968-04-05 1970-08-25 Becton Dickinson Co Micropipette holder
US4023716A (en) * 1976-04-20 1977-05-17 Justin Joel Shapiro Micro-dispensing liquid pipet
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US4340390A (en) * 1980-06-16 1982-07-20 Eastman Kodak Company Method and apparatus for metering biological fluids

Cited By (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4951512A (en) * 1988-06-23 1990-08-28 Baxter International Inc. System for providing access to sealed containers
US5059393A (en) * 1989-01-05 1991-10-22 Eastman Kodak Company Analysis slide positioning apparatus and method for a chemical analyzer
US20050170340A9 (en) * 1989-06-07 2005-08-04 Affymetrix, Inc. Arrays for detecting nucleic acids
US20030003475A1 (en) * 1989-06-07 2003-01-02 Affymetrix, Inc. Arrays for detecting nucleic acids
US20030119011A1 (en) * 1989-06-07 2003-06-26 Affymetrix, Inc. Arrays for detecting nucleic acids
US5171531A (en) * 1989-10-25 1992-12-15 Hewlett-Packard Company Apparatus for automatic delivery of a vial to an automated sampling system
US5089229A (en) 1989-11-22 1992-02-18 Vettest S.A. Chemical analyzer
US5336467A (en) 1989-11-22 1994-08-09 Vettest S.A. Chemical analyzer
US5250262A (en) 1989-11-22 1993-10-05 Vettest S.A. Chemical analyzer
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Publication number Publication date
EP0180494A1 (fr) 1986-05-07
FR2571147B1 (fr) 1986-11-14
EP0180494B1 (fr) 1989-03-22
JPH0320707B2 (fr) 1991-03-20
JPS61262664A (ja) 1986-11-20
FR2571147A1 (fr) 1986-04-04
DE3569032D1 (en) 1989-04-27

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